Process of reactivating a silicaalumina cracking catalyst



f n ti al *--2, 4so,sz1"

' to seriously impair the'catalytic efliciency of the metal and washing the catalyst free of said salt.

referred to as contamination. is fairly rapid, it be- Ernest A. Bodkin, Mickleton, and James M. Johnson, Woodbury, N. 1., assignors to Soconr-Vacnum Oil Company, Incorporated, a corporation of New-York I No Drawing. Application June 8, 1945,

i Serial No. 597,968

1 Claims. (Cl. 252- 12) umrao STATES PATENT OFFICE.

This invention relates to a process for reacticatalyst maybein service for 15,000 thirty-minute vating catalysts used in the conversion of hydrocycles before becoming so degenerated as to recarbons wherein the vapors of a hydrocarbon quire replacement. For example, a year or more charge stock are contacted at conversion condimay elapse before a catalyst drops from an initions of temperature and pressure with a solid 5 tial activity of 38.5. as hereinafter defined, to 2'5 adsorbent conversion catalyst comprising essenor 30. This slow degeneration will be referred to tially silica and alumina. More particularly, the a's deactivation to distinguishit from contaminainvention is concerned with a process in which a tion. 1 catalyst which has suii'ered serious deterioration 1 The commercial practice in the past has been of activity is reactivated by a novel method of t'o discard a deactivated hydrocarbon conversion treatment hereinafter described. v 1 catalyst and employ a fresh charge of new cata- Processes of catalytic conversion of the type to iyst. .By means of the present invention, this pracwhich this invention 'pertainsare well known in tice can be substantially eliminated and the low the art. Thus, in the catalytic cracking of petroactivity catalyst renewed to approximately its leum hydrocarbons, a porous adsorbent aluminum original activity by the particular chemical treatsilicate clay or synthetic silica-alumina catalystment described herein. It is accordingly the priis contacted with hydrocarbon vapors at convermary object-of this invention to return a deactision conditions, for example, 800 F. to 1000 F. at I vated. catalyst to a higher activity level. atmospheric or greater pressures. 'The reaction The reactivation is brought about by introduc-- which takes placeis essentiallya cracking to proing a zeolitic alkali metal into the deactivated duce lighter hydrocarbons, but is accompanied catalys't and subsequently replacing the alkali by a number of complex side reactions such as metal in a base-exchange operation with a metal aromatization, polymerization. alkylation and the designed to increase the hydrocarbon conversion like. As a result of these complex reactions. 9. efllciency of the catalyst. This is accomplished by carbonaceous deposit is laid down on the catalyst soaking the deactivated catalyst in an aqueous sowhichv is commonly called coke, although it lution of an alkali' metal compound, preferably contains considerable hydrogen and is ill l ll' the hydroxide orsilicate. base exchanging the a highly condensed hydrocarbon. The coke tends alkali-treated catalyst with a salt of the desired catalyst for the principal reaction and the con- The present invention has established that an version reaction is therefore suspended after alkali metal introduced into a deactivated silicac k t th ex nt 1' a few per cent by We of alumina catalyst, which. may be either a natcatalyst, has accumulated on the catalyst. The urally occurring clay typified by superflltrol clay catalytic surface is th n r n r by burning and fullers earth of a synthetic silica-alumina the coke in a stream of oxidizing gas and the composite, is base exchangeable and can be recatalyst is returned to the conversion stage of placed by various other metals such as aluminum, the cycle. zirconium, thorium, and beryllium to yield hydro- The catalyst also undergoes a second type of carbon conversion cam] was a rene ed degeneration by reason of changes in the catalyst tmty. ysts ha w itself as contrasted with the masking of catalytic The activity of the catalyst is a measure of its surfaces by coke demsit- As the catalyst is capacity to catalyze conversion of hydrocarbons carried through a large number of cycles of aland as used throughout the specification and ternate conversion and regeneration, the activity claims is expressed as the percentage conversion following each regeneration becomes progressively of Light East Texas Gas on having an A P L rless until the activity is too low for economical 4o gravity or and a bomng range of 418 to use of the catalyst. These two types of degen'eration difier in the time factor as well asin the to gasoline having an end point of by nature of the change occurring. Coke deposition,

passing vapors of said gas oil through the catalyst ing desirable to remove the coke by burning after about 10 to 20 minuteson stream. This burning of catalyst per hour of the coke will be hereinafter designated as re- The Wm to illustrate generation. On the other hand, the change in fi 1 basic. nature of the catalyst, resulting in lowered 1 1- mm activity after regeneration, is a slow change. A A silica-alumina clay cracking catalyst having 1 anoriginalactifl y 28.9. A volume o! 800 its activity after a recc. of this deactivated catalyst was soaked in 2'50 cc. of a 4% by weight,

solution sodium hydroxide torzihours at room temperature. and then water washed free or caustica The sodium content oithe caustic-tree 4 i' havin an activity of 28.9 was soaked in 300 cc. 01 an 11.1% by weight solution of "11 brand sodium silicate for 24 hours at room-temperature. Alter soaking, the catalyst was treated with'three applications or aluminum sulphate as in Example 1 and washed with 209 cc. of water each hour for- '75 hours until free from soluble sulphate. The catalyst was dried: and found-to have an activity of with a second application of 250 cc. of 19.5% aluminum sulphate for again and given a another 4 hours, then drained third application of aluminum sulphate for a similar period of time, The catalyst was then washed with 200 cc.

tree from soluble sulphate.

hour tor 80 hours until 0! water each The catalyst was dried and heated to a temperav catalyst at this point was 0.11%. The catalyst 39.3. g

' then was treated with 250 00.010. 19.5% by weight 10 Further examples are given in-the following solution of aluminum sulphate for a period c; 4 table:

' Tm: I

ted 04mm Example 1 13m- 5:3, s 4 s 0 *7 s 0 10 Treatment Vol.0iCata-iyst, 100 000 300 000 300 e00 000 000 $gi1 cm 107 47 77 107 1117 10 17 21 07 i'im sodii'im sooiiim sodiiim sm'iiufn soi'iiui'ii soiiiufii V Hydroxide Hydroxide Hydroxide Hydroxide Silicate Silicate Silicate Vol. 0! Soaking 80in,

00-. 200 250. 250 250 2,50 250 250 'rimcoismkmn 24 4s 12 0 12 4s 0 Base Exchange 80111., I

Per Cent Wt. .01

(so- 10.5 10.5 10.5 10.0 10.0 10.0 10.0 10.0 Vol. of 80111. per Application, m 200 200 250 200 200 200 250 250 Number 0! Appiieatioltiitn umewA s a a a s s a a 'rr 11- plication Hrs. 4 4 4 4 4 4 4 4 Vol. oi ster per Henri Washin 200 000 200 a 200 200 200 200 200 Total asking T ime,

m. V 104 e0 05 7s 0s 7a 100 so Propertiuof analyst mari a 0on4"-.- 0.040 0.000 .700 .070 .070 .002 .700 .000 .724 .000 Coke or Cent When v Charge".-. 0.4 as 4.0 4.2 3.7 as as 4.2 as as Gas Per Cent Wt. on

Charg as as 0.4 a0 4.7 4.7 as 00 a7 3.7 Activity 7 sec 28.9 40.7 00.4 38.1 30.0 36.8 00.0 ass 30.7 hours. The catalyst was drained and treated Inother exampies,adeactivated silica-alumina clay catalyst having an activity of 30.0 was reactivated by soaking in sodium hydroxide solution, washing free of caustic and base exchanging with various solutions. The base-exchange operation was carried out in eight separate soaking periods of three hours each. The results are shown below, the general procedure being carried out as in ture of 105071'. Upon analysis. it was found that Example 1.-

' i Tm! 11 l tai y s t Example mm 11 12 13 14 lo 16 17 Treatment Book 1114 4. SodinmH 0410400111.:

s king fig. in. ya: 24 5 min. 24 24 24 24 24 vol. 80in. v01. can on; 1.1 1.1 1.1 1.1 1.1 1.1 1.1 Base Exchangi Chemical o 4.144504), Amsoo; T110100. msooi 300N001 LlCl Cone. of Exchange 80in. Per Cent W 21.6 21.6 30. ii 18. 7 30. 5 19. 2

Total v01. in. v01. Catalyst as as as as 3.3 3.3

Total Exchange r 24 24 24 24 24 24 Water Washing:

Washing Time, 1114.- s1 .50 s0 s0 50 s0 00 Total v01. in. per v01. Catalyst 140- 130 140 100 130 Properties oi Catalyst:

w, gmJec 0.72 0.00 0.71 0.70 0.72 0.70 0.00 0.08

Gas, Per Cent weas 1.1 4.8- 0.4 4.2 5.1 0.0 1.1

Coke. Per Cent Wta 0 1. 0 3.0 a 0 as 3.1 a. 0 1. 0

Activity 00.0 14.0 02.0 sea 04.1 sec 00.3 20.3 the sodium content of the catalyst had been re- From the above examples, it will be seen that duced to 0.05% as a result oi the base exchange with aluminum sulphate.

vated catalyst was 37.9.

The activity of reactinxmnna ii volume of 3001 cc.

alumina clay catalyst similar to that 0! Example oi! a deactivated silica 1 I6 the ciay catalyst due to Concentrations 15% by weight may be used. The use of sodium hydroxide solutions ofv concentrations greater than 15% by weight results in disintegration of partial decomposition of In general, a solution of soa concentration of 4% to 5% alumina-silicates. dlum hydroxide at by weight is preferable for the purposes of the inreactivated may be permitted to soak for as long as 72 hours. It should be noted from Example 12 in Table II, in which the deactivated catalyst was treated with a 4% by weight solution of sodium hydroxide for 5 minutes, washed free of caustic and then exchanged with A12(SO4)3, that the activity was improved only slightly, indicating that the soaking period is essential if the improved results of this invention are to be obtained.

Sodium silicate has also been used as the soaking solution in concentration of from about 10% to about 25% by weight. Commercial N brand sodium silicate containing 8.9% NazO, 28.7% SiOz and 62.4% H2O by weight was employed in preparing the solutions, although other types of sodium silicate could likewise be used. The concentrations of sodium silicate are limited only by the convenience of handling, however, aqueous solutions containing 11% to 15% by weight proved preferable. The time of soaking, as in the case of sodium hydroxide may vary overa wide range, some improvement being obtained with a soaking period as low as one hour. The soaking period yielding the best results was about 48 hours.

For purposes of comparison, Example 10 was carried out omitting the soaking treatment; that is, the deactivated catalyst was treated directly with a 19.5% by weight solution of AI2(SO4)3 for a total period of 12 hours, then washed free of sulphate, dried and heated to a temperature of 1050 F. The improvement in the reactivated slight, thus establishing the omitted, the deactivated clay catalyst being treated with a 4% by weight sodium hydroxide solution for 24 hours, washed free of caustic and dried. The activity of the treated catalyst was so low as to be ineffective for practical use. Thus, both soaking in an aqueous solution of an alkali metal compound an the base-exchange operation are essential to reactivate a spent hydrocarbon conversion catalyst in accordance with this invention.

The salts of various metals may be employed as base-exchange solutions. Thus. salts of berylthorium,,z1rconium and aluminum have been used. The metallic salts employed are those ofpolyvalent metals. A monovalent metal salt, for example, lithium chloride, used in Example 17 in the base-exchange operation, did not yield the improved results of this invention. Aluminum sulphate may be used in concentrations up to 30% by weight as the base-exchange solution, although solutions of about 18% to 20% by weight have proved preferable. The extent of base ex change may vary over a period of from 1 to 72 hours. A 24 hour period of base exchange was found to be convenient and to yield excellent results and therefore is preferred.

In the reactivation of the spent aluminasilica catalysts using a sodium silicate solution and aluminum sulphate, a reactivated catalyst having a physical hardness appreciably higher than its hardness prior to the chemical treatment 5 while the hardness index the following structural formulas:

Clay Catalyst Silica alumina Synthetic catalyst Under service conditions, various influences and outside factors tend to diminish the catalytic properties of the catalysts. Among these are the gradual incorporation into the catalytic strucsynthetic catalyst Treatment with sodium hydroxide or sodium silicate solution of the catalysts Whose activity depreciated with use can be restored by first substituting sodium in place of the harmful element, thus restoring its zeolitic activity, and secondly displacing sodium in the zeolite, so formed, by an .catalyst had been cate the catalyst treated with 7% lIaOH and ictive element such as aluminum. These mechmisms are believed to proceed as follows:

Substitution of active aluminum for the sodium introduced into the catalyst structure by the treatment with sodium hydroxide or sodium silicate is accomplished by a subsequent treatment with aluminum sulphate solution. The mechanism is apparently identical with the one pictured above.

From the previous discussion, it becomes apparent that the ability of the catalysts to be reactivated is intimately related to their ability to function as zeolites. To further establish that the replacement of sodium ions with aluminum ions wasproceeding by a base-exchange process, an experiment was carried out as follows: One thousand cubic centimeters of crushed deactivated claycatalyst having a sodium content of .066% was treated with a 7% solution of sodium hydroxide and then water washed at a rate of 20 cc. per minute for 67 hours until a pH of 9.5 was reached. A 100 cc. sample of this treated catalyst was analyzed for sodium at this point and found to contain 0.32% sodium. A second 100 cc. sample was water washed for an additional 75 hours at the rate of 1.33 cc. per minute until a pH of 8.8 was reached. The catalyst was then dried, and tempered at 1050 F. for one hour. The sodium content of this sample was 0.29%. A

third sample of 550 cc. was soaked in 370 cc. of

16% by weight of aluminum sulphate for 24 hours at room temperature and then water washed at a rate of 11% cc. per minute for 42 hours'until the catalyst was free of sulphate. This sample was dried, tempered-at 1050" F. for one hour and upon analysis was found to contain 0.12% sodium. Thus, the sodium content of reduced 59% and this quantity of sodium replaced by aluminum in a baseexchange process.

An additional interesting experiment to show that caustic treatment effects the incorporation of base-exchangeable sodium in the clay catalyst was carried out by employing the catalyst as a water softening agent, and determining the amount of calcium carbonate removed per cubic foot of catalyst. This measurement, would indiquantity of zeolitic sodium in the catalyst which could be replaced by calcium ions. The results are summarized in the following table:

Bass Excnsncn CArAcrrY or CLAY CATALYST Grains CaCO: per cubic foot of catalyst Unused catalyst -1 1388 Used cataly 1103 shed free of NaOH 3969 The base exchange capacities of the catalysts were determined by a test consisting of passing 'cent by weight of alkali metal hydroxide, re-

moving the catalyst from contact with the soaking solutions, water-washing the catalyst free of said solution, directly base exchanging the alkali metal so introduced into said catalyst with an aqueous solution of an aluminum salt and washing the catalyst free of said salt.

2. A process for reactivating a deactivated silica-alumina hydrocarbon conversion catalyst, comprising soaking the deactivated catalyst for a period of at least about one hour in an aqueous solution containing from about 1 to about 15 per cent by weight of alkali metal hydroxide, removing the catalyst from contact with the soaking solution, water-washing the catalyst free of said solution, directly base exchanging the alkali metal so introduced into said catalyst with an aqueous solution of a beryllium salt and washing the catalyst free of said salt.

3. A process for reactivating a deactivated silica-alumina hydrocarbon conversion catalyst, comprising soaking the deactivated catalyst for a period of at least about one hour in an aqueous solution containing from about 1 to about 15 per cent by weight of alkali metal hydroxide, removing the catalyst from contact with the soaking solution, water-washing the catalyst free of said solution, directly base exchanging the alkali metal so introduced into said catalyst with an aqueous solution of a zirconium salt and washing the catalyst free of said salt.

4. A process for reactivating a deactivated sillea-alumina hydrocarbon conversion catalyst, comprising soaking the deactivated catalystfor a period of at least about one hour in an aqueous-solution containing from about 10 to about 25 per cent by weight of alkali metal silicate, removing the catalyst from contact with the soaking solution, water-washing the catalyst free of said solution, directly base exchanging the alkali metal so introduced into said catalyst with an aqueous solution of an aluminum salt and washing the catalyst free of said salt.

5. A process for increasing the activity of a catalytic composition useful in hydrocarbon conversion operations, which comprises soaking a silica-alumina composite for a period of at least about one hour in an aqueous solution of an inorganic alkaline alkali metal compound, the concentration of which varies inversely with its alkalinity, said concentration being sufficient to effect the introduction of alkali metal into said composite but not exceeding about 25 per cent by weight, removing the composite from contact with the soaking solution, water-washing the composite free of said solution, base exchanging the alkali metal so introduced into said composite with a salt of a polyvalent metal and washing the resulting catalytic composition free of said salt.

6. A process for increasing the activity of a catalytic composition useful in hydrocarbon conversion operations. which comprises soaking a silica-alumina composite for a period of at least about one hour in an aqueous solution of an alkali metal hydroxide of concentration not exceeding about 15 per cent by weight but suflicient to efiect the introduction of alkali metal into said composite, removing the composite from contact with the soaking solution, water-washing the composite free 01 said solution, base exchanging the alkali metal so introduced into said composite with a salt of a polyvalent metal and washing the resulting catalytic composition free of said salt.

7. A process for increasing the activity of a catalytic composition useful in hydrocarbon conversion operations, which comprises soaking a silica-alumina composite for a period of at least about one hour in an aqueous solution of an alkali metal silicate of concentration not exceeding about 25 per cent by weight but sufficient to efiect the introduction of alkali metal into said composite, removing the composite from contact with the soaking solution, water-washing the composite free of said solution, base exchanging 10 the alkali metal so introduced into said composite with a salt 01' a poiyvalent metal and washing the;: resulting catalytic composition free of said sal ERNEST A. BODKIN. JAMES M. JOHNSON.

REFERENCES CITED The following references are of record in the 10 file of this patent:

UNITED STATES PATENTS 

